Surface active compounds



Patented Sept. 22, 1953 SURFACE ACTIVE COMPOUNDS William B. Hughes,Bartlesville, kla., assignor to Cities Service Oil Company,Bartlesville, 0kla., a corporation of Delaware No Drawing. ApplicationJune 14, 1950, Serial No. 168,160

Claims.

This invention relates to new compositions of matter having surfaceactive properties and more particularly to certain amine salts ofsubstituted naphthalene sulfonic acids which are particularly useful inthe breaking of emulsions such as oil field emulsions.

Reference is made to my copending applications Serial No. 131,699 filedDecember 3, 1949, and Serial No. 168,159, filed concurrently herewith(both now abandoned), in which the compounds of the present inventionare disclosed but not claimed.

One of the most troublesome problems met with in crude oil productionrelates to the breaking of water-in-oil emulsions formed in wellsproducing both water and brine. These emulsions are generally of twotypes, the first type a mechanically cut emulsion, which is usuallyformed in the well by faulty pumping equipment, the other type being agas-cut emulsion, the formation of which is aided by the emulsifyingaction of certain asphaltenes and other chemical emulsifiers present inthe crude oil. The emulsion commonly encountered is a mixture of both ofthese types, and its properties will vary from well to well, and evenfrom day to day in the same well. Unless these emulsions can beeffectively and completely broken, the oil content is lost. It is alsodesirable that the emulsion be broken as rapidly as possible, in orderto keep the number and size of the settling tanks to a minimum.

There are apparently two phases of an emulsion resolving problem. Thefirst involves a surface phenomenon in which the oil film surroundingthe water particles of micron size is weakened, allowing the particlesto coalesce into larger droplets. This phase will be hereinafterreferred to as the emulsion breaking step. The other phase involves thesplitting of the broken emulsion into separate oil and water phases.This phase will be referred to as the water separation step.

It will be evident from the foregoing that the ideal emulsion resolvingagent must be effective to break both mechanical-cut and gas-cutemulsions with substantially equal facility, must rapidly break theemulsion, and must be eifective in causing rapid water separation fromthe broken emulsion. The agent must also be eifective in very smallconcentrations, in order to hold the treating cost to a minimum. Manyemulsion resolving agents have been proposed in the past, but none ofwhich I am aware are effective to accomplish all of the desired results.Thus one agent may be effective to break gas-cut emulsions, but not themechanical-cut type; another may be a good emulsion breaker but havepoor water separation qualities; while still another may show good waterseparation qualities but may fail to break the emulsion completely.

It is an object of this invention to provide a series of compounds whichwill rapidly resolve emulsions of all types, giving rapid break andcomplete water separation.

It has been found that emulsion resolving agents which will accomplishthe foregoing object may be produced by neutralizing to a methyl orangeend point a carbonyl-polyamine condensation product with a propylatednaphthalene sulfonic acid.

The condensation product which I use as an intermediate in thepreparation of these new compounds is prepared by reacting one mol of analdehyde or a ketone with two mols of an amine. The exact structure ofthe resulting compound is not known since there are a number ofpossibilities, depending upon which nitrogen hydrogen of the aminereacts with the oxygen atom of the carbonyl. For example, if diethylenetriamine were to be reacted with formaldehyde, it Would be possible tohave compounds of the following theoretical structures:

While it is believed that the terminal nitrogen of the polyamine wouldprobably be the most reactive, to give the structure shown in Formula I,I do not wish to be limited to this particular structure since otherstructures are possible from the reaction.

When the amine and an aldehyde are mixed, the reaction commencesspontaneously and Will normally go to completion at room temperatureswithin a matter of a few hours. I have found it desirable, however, toheat the mixture in order to speed up the reaction and to insure that itgoes to completion. When heated to about C. the reaction is complete inabout one-half hour. The product, an oily liquid, may then be separatedfrom the water formed in the reaction by any suitable method such ascentrifuging or decanting. When using a ketone as a reagent instead ofan aldehyde, the reaction is slower and ethylene pentamine may be usedwith apparently very similar results.

The nature and molecular weight of the carbonyl component of my newcompounds is not critical, and may be alkyl, aryl, or heterocyclic. Forexample, I have obtained good results when using formaldehyde,acetaldehyde, benzalde-- hyde, heptaldehycle, and ethyl hexaldehyde, andamong the ketones, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, and methyl isobutyl ketone. I do notwish,however, to be limited in the practice of my invention to the abovespecifically mentioned aldehydes and ketones, since any aldehyde orketone is apparently satisfactory.

The propylated naphthalene sulfonic acid which I use as the neutralizingagent for my intermediate compounds may be prepared according to thedirections given by Walker in U. S. Patent No. 1,873,165. The compoundhas the formula:

in which Z is an isopropyl radical and n is a whole number from 1 to l.Other organic acids, such as stearic acid and petroleum green acids havebeen tried as neutralizers, but the products are far infereior inemulsion-breaking qualities.

The propylated naphthalene sulfonic acid is preferably used in a molarequivalent with the number of nitrogens present in the carbonylamineintermediate condensation product. For example, if diethylene triaminewere used as the amine component the intermediate product would beneutralized with 6 mols of propylated naphthalene sulfonic acid, whereasif tri'ethylene tetramine were used, 8 mols of the acid would benecessary to neutralize the compound to a methyl orange end point.Neutralization is accompanied by the evolution of considerable heat, andby a definite color change from light brown to dark brown, the finalproduct being a viscous liquid. This product may be used as such butsince it is generally too viscous for injection into oil gatheringlines, I prefer to dilute it to the proper viscosity with kerosene orother suitable mineral oil.

The various products produced as described above have been subjected tovarious tests, both in the field and in the laboratory, and'have provenoutstanding in breaking petroleum water-in-oil emulsions, such as arecommonly met with in oil production. While the effectiveness of thesecompounds will vary from well to well, depending upon the emulsionproduced by the particular well, it has been found that excellentresults have been obtained when the products are used in concentrationsas low as 150 parts per million, and they are in general very superiorin effectiveness to the best of the commercial breakers now on themarket.

Having now described my invention, what I claim as new and useful is: 1.The process of resolving emulsions including subjecting'a petroleumwater-in-oil emulsion to the action of a composition consistingessentiallyof the reaction product of one mol of a carbonyl selectedfrom the group consisting of aldehydes and ketones and two mols of apolyethylene amine, neutralized to a methyl orange endpoint with apropylated naphthalene sulfonic acid,

2.. The process of resolving emulsions including subjecting a petroleum'water-in-oil emulsion to the action of a composition consistingessentially of the reaction product of one mol of a carbonyl selectedfrom the group consisting of aldehydes and ketones and two mols ofdi'ethylene triamine, neutralized to a methyl orange end point with 'apropylated naphthalene sulfonic'acid.

3. The process of resolving emulsions including subjecting a petroleumwater-in-oil emulsion to the action of a composition consistingiessentially of the reaction product of one mol of a carbonyl selectedfrom the group consisting of aldehydes and ketones and two mols oftriethylene tetramine, neutralized to a methyl orange endpoint with apropylated naphthalene 'sulfonic acid.

1. The process of resolving emulsions *mclu'ding'subjecting a petroleumwater-in-oil'emulsion to the action of a composition consistingessentially of the reaction product of one mol ofa carbonyl selectedfrom the group consisting-of aldehydes and ketones and two mols oftetraethylene pentamine, neutralized to a-methyl orange end point with apropylated naphthalene sulfonic "acid.

5. The process of resolving emulsions including subjecting a petroleumwater-.in-oil emulsion to the action of a composition consistingessentially of the reaction product of one mol of a carbonyl selectedfrom the group ziconsisting of formaldehyde, acetaldehyde, benzaldehyde,heptal'dehyde, ethyl hexaldehyde, acetone, methyl ethyl ketone, diethylketone, .di tisopropyl ketone, acetophenone, and methyl iscbutyl ketone,:and two mols of a polyethylene amine, :neutralize'd to a methyl orangeend pointwithapropylated naphthalene .sulfonic acid.

LB. HUGHES.

References Cited in the file of this patent UNITED STATES PATIENTSNumber Name Date 2,083,224 'De Groote June '8, 1937 2,083,225 De GrooteJune "8, "1937 2,110,837 'Blair Mar. "8, 1938 2,223,935 Daniels et a1Dec. 3, 1940 2,250,407 De Groote et a1 J uly'22, 1941

1. THE PROCESS OF RESOLVING EMULSIONS INCLUDING SUBJECTING A PETROLEUMWATER-IN-OIL EMULSION TO THE ACTION OF A COMPOSITION CONSISTINGESSENTIALLY OF THE REACTION PRODUCT OF ONE MOL OF A CARBONYL SELECTEDFROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES AND TWO MOLS OF APOLYETHYLENE AMINE, NEUTRALIZED TO A METHYL ORANGE END POINT WITH APROPYLATED NAPHTHALENE SULFONIC ACID.